Water-soluble thiazolyl monoazo-dyestuffs



United States Patent US. Cl. 260-158 6 Claims ABSTRACT OF THE DISCLOSURE Water-soluble monoazo-dyestuffs and a process for their preparation and especially to dyestuffs of the general Formula 1:

wherein A represents a radical of the benzene and naphthalene series, X represents a grouping linked to A and/or B of the formula Wherein R represents a hydrogen atom or an alkyl radical containing from 1 to 4 carbon atoms and Z represents an inorganic or organic radical which may be split off by an alkaline agent, R represents a alkyl, carboxy or carbalkoxy group, m represents an integer from 0 to 3, n represents the number 0 or 1 and p represents the number 1 or 2, suitable for the dyeing of textile materials especially of those of wool, silk, natural or regenerated cellulose or polyamide fibers.

The present invention relates to new valuable watersoluble monoazo-dyestufifs and to a process for their preparation; it relates especially to dyestuffs of the general Formula 1 wherein A represents a radical of the benzene or naphthalene series, X represents a grouping linked to A and/or B of the formula 3,468,873 Patented Sept. 23, 1969 "ice wherein R represents a hydrogen atom or an alkyl radical containing from 1 to 4 carbon atoms and Z represents an inorganic or organic radical which may be split off by an alkaline agent, R represents an alkyl, carboxy or carbalkoxy group, m represents an integer from O to 3, n represents the number 0 or 1 and p represents the number 1 or 2.

These dyestuffs can be prepared by diazotizing 1 mole of an amine of the general Formula 4 wherein A represents a radical of the benzene or naphthalene series, X represents a grouping of Formulae 2 and 3 mentioned above or a grouping of Formula 5.

N nSOgCH2CHgOH (5) m represents an integer from 0 to 3 and p represents 0 or 1, and coupling it with 1 mole of an azo component of the general Formula 6 HOJTERI wherein R has the above-mentioned meaning and X represents a grouping of formulae 2, 3 and 5 mentioned above m and p represent 0 or 1 and the benzene nucleus B may contain further substituents, and the diazo and azo components are to be chosen in such a way that the sum of m and m is 0 to 3 and the sum of p and p is 1 or 2; in the case that one of the components contains grouping is converted into the corresponding sulfuric acid a grouping of the above-mentioned Formula 5, this ester group.

Radicals Z, which may be split off by an alkaline agent are, for example: halogen atoms, such for example as chlorine or bromine atoms, an alkyl-sulfonic acid ester group with an alkyl group containing, for example, from 1 to 4 carbon atoms, or an aryl-sulfonic acid ester group such for example as an ester group of the benzeneor naphthaline-sulfonic acid, or an acyloxy group, such for example as the acetoxy group, furthermore a phenoxy or a dialkyl-amino group, such for example as the dimethyl or diethyl-amino group, the thiosulturic acid ester group and especially the sulfuric acid ester group.

In addition to one of the aforementioned groupings of Formula 2 or 3 and the sulfonic acid group the aromatic nuclei A and B may contain substituents usual in azodyestufts, such for example as lower alkyl, lower alkoxy, carboxyl, nitro, sulfamido, carb-lower-alkoxy, N,Ndilower alkyl sulfamido, chlorine, bromine or acetylamido.

The conversion of the groups of Formula 5 into the corresponding sulfuric acid ester groups may be effected in different ways, for example by treating them with concentrated sulfuric acid, monohydrate or sulfuric acid or chlorosulfonic acid or with amidosulfonic acid in the presence of a tertiary organic hydroxide solution, such as pyrridine or a picoline.

The monoazo-dyestuifs with a grouping of Formula 3 described above may also be prepared by modifying the process, i.e. by converting subsequently the grouping of Formula 2 contained in the monoazo-dyestulf obtained according to the process of the present invention into the grouping of Formula 3. A grouping of Formula 2 contained in the monoazo-dyestuffs, obtained according to the process of the present invention may, for example, be converted into a B-thiosulfato-ethyl-sulfonic group by means of salts of the thiosulfuric acid or into a 3-dia1kyl-aminoethylsulfonic group by the action of a dialkyl amine.

In addition to this, the monoazo-dyestufi's with a grouping of Formula 2 may also be prepared when modifying the process, by converting subsequently the grouping of Formula 3 contained in the monoazo-dyestuff obtained according to the process of the present invention by means of alkaline agents, such for example as an aqueous sodium hydroxide solution, into the grouping of Formula 2.

The Z-aminothiazole or Z-amino-naphthiazole derivatives, used as diazo components, are obtained from the correspondingly substituted anilines or naphthyl amines by reacting them with alkyli thiocyanates in the presence of an oxidizing agent.

Thus, for example, the 2-amino-benzthiazole-6-sulfonic acid is obtained in stoichiometric quantities at a very good yield, by reacting sulfanilic acid in an aqueous mineral acid suspension with alkali thiocyanate in the presence of iron (III) or copper (II) salts. The diazotization is preferably effected in sulfuric acid with nitrosylsulfuric acid as diazotizing agent.

The monoazo-dyestutfs obtained according to the present invention show a high tinctorial strength and are valuable dyestuffs for the dyeing of wool, silk and polyamide fibers. They are dyed in an acid, neutral or weakly alkaline bath. They are also especially valuable as reactive dyestuifs for dyeing and printing cotton and other natural or regenerated cellulose fibers. When dyeing such fiber materials the dyestuffs are used according to printing or dyeing processes in connection with a treatment of acidbinding agents, such as sodium hydroxide, sodium carbonate or sodium bicarbonate.

Processes of this kind are shown from the more recent literature (cf. Melliand Textilberichte 1959, 539 and 1965, 286). According to these processes especially cellulose textile materials can be dyed in deep golden yellow to red orange shades, which show a far better fastness to wet processing than dyeings of comparable shades with direct dyestuffs. When dyeing cellulose materials the new dyestuffs prove a good afiinity. When printed on cotton the dyestuffs show extraordinarily sharp contours of the print, especially by carrying out the modern economical processes, for example with the rapid thermosetting process as well as with the two-phase printing (cf. Melliand Textilberichte 1962, 265 as well as Textilpraxis 1965, 594).

The following examples serve to illustrate the invention but they are not intended to limit it thereto; the parts being by weight unless stated otherwise.

EXAMPLE 1 7.35 parts of 2-amino-6-(N-methyl-N-ethionyl)-aminobenzthiazole were dissolved in 100 parts of semiconcentrated sulfuric acid at a temperature of 40 C. The solution obtained was cooled and, after addition of 6.05 parts of nitrosylsulfuric acid of 42% strength at 10 to C., stirred for 2 hours at 0 C. After having destroyed the nitrosylsulfuric acid in excess by means of amidosulfonic acid a neutral solution of 5.16 parts of 1-(4-sulfophenyl) 3-methyl-5-pyrazolone in 25 parts by volume of water was added and the pH was adjusted to 6 by 630 parts by volume of a sodium carbonate solution of 10% strength. When the coupling was terminated the batch was salted out with of potassium chloride (referred to the volume of the solution), filtered off and washed with a potassium chloride solution of 15 strength. The dyestuff, which corresponds in the form of free acid to the formula was dried in vacuo at 60 C.

An orange powder was obtained which is easily soluble in water with the same color and which yields on cellulose fibers in the presence of an alkaline agent strong, golden yellow prints and dyeings of good fastness to Wet processing.

When printed according to the two-phase process excellent sharp contours were obtained.

EXAMPLE 2 28.7 parts of 2-amino-6-(N-methyl-N-p-oxethylsulfonyl)-amino-benzthiazole were dissolved in 200 parts of semi-concentrated sulfuric acid at room temperature. At a temperature in the range of from 0 to 5 C., 36 parts of nitrosylsulfuric acid of 40% strength were added and stirred for 2 hours. After having destroyed the nitrosylsulfuric acid in excess a neutral solution of 28.6 parts of 1-(4'-sulfophenyl)-3-methyl S-pyrazolone in parts by volume of water was added. By addition of 1,500 parts by volume of a sodium carbonate solution of 10% strength the pH was adjusted to 4 to 5. After stirring for several hours the dyestuff precipitated. It was filtered off, washed with a sodium sulfate solution of 20% strength and dried. The whole dry product was introduced into parts of sulfuric acid monohydrate at a temperature of 10 to 15 C. and stirred for 15 hours at room temperature (20 to 25 C.). The viscous mixture was then decomposed on 1,000 parts of finely crushed ice and adjusted to a pH value of 6 by means of parts of anhydrous sodium carbonate. The dyestuff was separated with 15% of potassium chloride (referred to the volume of the solution), filtered off and washed with 100 parts of a potassium chloride solution of 15% strength.

The dyestuff is identical to that described in Example 1.

EXAMPLE 3 7.95 parts of Z-amino S-methoxy 6-(N-methyl-N- ethionyl) -amino-benzthiazole were dissolved in 100 parts of semi-concentrated sulfuric acid at 40 C. and diazotized within 2 hours at 0 to 5 C. with 6.05 parts of nitrosylsulfuric acid of 42% strength. After addition of amidosulfonic acid in order to destroy the nitrosylsulfuric acid in excess, a neutral solution of 5.2 parts of 1-(4-sulfophenyl) 5-pyrazolone-3-carboxylic acid in 25 parts of water was added and adjusted to pH 6 with 620 parts by volume of a sodium carbonate solution of 10% strength. The dyestuff which could not be salted out was obtained by evaporating the solution in vacuo at 60 C. or by spray-drying. It corresponds in the form of free acid to the formula l SOzH The red-brown dyestutf powder is easily soluble in water and yields on cellulose fibers strong orange dyeings, fast to wet processing.

EXAMPLE 4 230 parts of Z-amino 6-sulfo-benzthiazole were dissolved in 400 parts by volume of concentrated sulfuric acid. 360 parts of nitrosylsulfuric acid were added at C. and the whole was then stirred for 30 minutes at a temperature within the range of from 0 to C. In the course of 90 minutes and at the same temperature 1,600 parts of finely crushed ice were added and the remainder of nitrosylsulfuric acid was destroyed by amidosulfonic acid. An ice-cold solution of 354 parts of 1-(4'-fi-hydroxyethylsulfonyD-phenyl 3-methyl 5-pyrazolone of 80% strength in 1,400 parts of water was then added to the resulting suspension of the diazonium salt; it was neutrally dissolved by the addition of 650 parts by volume of a Z-N-sodium hydroxide solution. In the course of 2 /2 hours the reaction mixture was then mixed with 1,200 parts of anhydrous sodium carbonate and, by addition of 8,000 parts of ice water, kept in a state which allows the stirring of the suspension. After having stirred the dyestuff suspension for hours it was heated up to 80 C.

The suspension was then slowly cooled off, filtered and dried in vacuo at 60 C. Within 3 hours the precipitated dyestuff was added to 900 parts by volume of concentrated sulfuric acid and stirred for 20 hours at room temperature.

The viscous reaction mixture was then added to 13,000 parts of ice/water while stirring and neutralized with 1,860 parts of anhydrous sodium carbonate. The dyestuff, which corresponds in the form of free acid to the formula HOaS precipitated without further addition of salt. Together with orange-red color, the dyestuff is soluble in water and yields on cotton, according to the two-phase and rapid thermosetting process, golden yellow prints of good fastness to wet processing and sharp contours.

EXAMPLE 5 708 part of 1-(4'-,3-hydroxy-ethylsulfonyl)-phenyl-3- methyl-S-pyrazolone of 80% strength were added at to C. to 100 parts of concentrated sulfuric acid and stirred for 15 hours at room temperature. The whole was then added to 2,000 parts of ice/water while stirring and neutralized by 106 parts of sodium carbonate. By the addition of parts by volume of concentrated sodium hydroxide solution, the pH was adjusted to 10 and the solution was stirred for 30 minutes until cold. The coupling solution thus obtained was given into a suspension of 46 parts of 2-amino-6-sulfo-benzthiazole which has been diazotized according to Example 4. The dyestutf precipitated without further addition of salt. In the form of free acid it corresponds to the formula The same dyestuff can be obtained by separating by the action of alkali hydroxide at room temperature 1 mole of sulfuric acid from the dyestuff described in Example 4.

EXAMPLE 6 50.5 parts of the dyestuff corresponding to the formula S O2C IIr-CHz-SSOsH In the presence of a sodium hydroxide solution the dyestutf yields on cellulose fiber material golden yellow dyeings and prints of good fastness to wet processing.

EXAMPLE 7 At a temperature of 45 C., 23 parts of Z-aminobenzthiazole-6-sulfonic acid were dissolved in 40 parts by volume of concentrated sulfuric acid, cooled at 0 to 5 C. and diazotized with 36 parts of nitrosylulfuric acid of 40% strength. After 30 minutes 200 parts of ice were carefully added at 10 C. and the nitrosylfuric acid in excess was then destroyed.

As azo component, 39.2 parts of the sulfuric acid ester of 1-(4-;9-hydroxyethylsulfonyl)-phenyl 5-pyrazolone-3- carboxylic acid were added in form of a neutralized aqueous solution (1,500 parts by volume). By the addition of parts of sodium carbonate the pH was adjusted to 7. When the coupling was terminated the dyestuii solution has been mixed with 15 parts of an aqueous diethylamine solution of 38% strength. In the course of 15 minutes, parts by volume of a 2N sodium hydroxide solution were then added and stirred for 1 hour at 50 C. and at a pH of 11. After cooling to room tems -c-N=N CH perature, the pH was adjusted to 6 by means of dilute i I hydrochloric acid and the dyestufi was salted out with Hols N H 10% of potassium chloride (referred to the reaction N volume). S0311 With orange-red color the dyestufi, which corresponds as free acid to the formula SO2 CH2CH2 OSO3II CN=N C O OH 11033 S HO N and presents a scarlet powder.

In the presence of sodium carbonate, it yields on cotton 1 full red-orange dyein-gs of good fastness to wet process- The dyestuffs, specified 1n the followlng table, may be prepared in a manner analogous to the examples given I above. On cellulose fibers they also yield dyeings and SOPCHFCHFMCHS prints of the already stated good fasmess properties.

Diazo component Azo component Tint 1 2-amino-6-(N-methyl-N-ethionyl)amino benzthiazole-.- l-(4-sulIo-phenyl)-5-pyrazolone-3-carboxylic acid Orange. 2 Amino-G-N-ethionyl-aminobenzthiazOle ..do Do. 3 2-amino-6-(N-methyl-N-ethionyl)-amino-benzthiazole 1-(2-chloro-5-sulfo-phenyl)-3-methyl-5-pyrazolone Golden yellow. 4.. do 1- '-methyl-4-sulfo-pheny1)-methyl-5-pyrazolone Reddish yellow. 5 1-(2,5-dichloro-4-su1fo-phenyl)-3-methyl-5-pyrazolone Golden yellow. 6 1- -nitropheny1)-5-pyrazolone-3-carboxylic acid Orange. 7 do 1-(Zignethyl-Q-sulfo-phenyl)-5-pyrazolone-3-carboxylic Reddish yellow.

8C1 8 Z-Eglliilgfi-(B-{lYdlOXY-QthYlSUlIOHYl-SUKIHIC acid ester)- 1-(4-sulfo-phenyl)-5-pyrazolone-3-carboxylic acid Do.

enz 13.20 e. 9 do 1-(4-su1fo-phenyl)-3-methy1-&pyrazolone Golden yellow. 10 2-amino-S-vinylsulfonyl-benzthiazo .d0 Do 2-amino-6-ethoxy-benzthiazole 12. Z-amino-F carboxy-benzthiazole do Reddish yellow.

13 2-arnino-4-methyl-benzthiazole-(S-sulfonic Golden yellow.

14 Z-amino-6-methyl-benzthiazole-i-sulfonic acid d D 15. 2-amino-trB-hydroxyethylsulfonyl-sulfuric acid ester- 1-(4-B-hydroxy-e D benzthiazole. phenyl)-3-methyl-5-pyrazolone.

16 z-amino-o-(N-methyl-N-ethlonyl)-amino-benzthiazole .do Do.

17 Z-amino-benzthiazole-fi-sulfonic acid 1(4-B-hydroxyethylsulfonyl-sulfurlc acid ester- Reddish yellow.

phenyl) -3 carboxy-5-pyrazolone.

18 .do 1-(4-B-hydroxyethylsulfonyl-sulfurlc acid ester-phenyl)- Golden yellow.

3-carbethoxy-5-pyrazolone.

19 2amino-naphtho(l,2)-thiazoIe-5-sulfonic acid 1-(4-B-hydroxyethylsulfonyl-sulfuric acid ester- Orange.

phenyl)-3-methyl-5-pyrazolone.

2o 2-amino-naphtho(2,1)-thiazole-&sulfonic acid do Do.

21 Z-amino-naphtho(2,1)thiazole-7-sulfonic acid... do

22 2-am1no-naphtho(2,l)thlazole-4,7-disulionic acid- Do.

23 2-aminonaphtho(2,1)thiazole-5,9-disu1fonic acid. Do.

24 Z-amino-naphtho(2,1)thiazole-6,8disulfonic acid- 25 2-amino-naphtho(2,1)thiazole-7,9-disulfonic acid. D

26 2-amino-naphtho(2,1)thiazole-4,7,9-trislllf0nic acidd0 Do.

27 2-amino-naphtho(2,l) thiazole-7,9-di-sulfonic acid 1-(4-fl-l1ydroxy-ethylsulfonyl-sulfuric acid ester Scarlet.

phenyl)-3carboxy-pyrazolone.

is easily soluble in water and forms a printing paste We claim:

which is very resistant to alkalies. On cotton, it yields 50 1. The water-soluble monoazo-dyestuff of the formula orange-red dyeings of good fastness to wet processing. [803mm EXAMPLE 8 S At a tempertaure of 30 to C., 36 parts of Z-aminonaphtho [2,1] thiazole-4,8-disulfo acid were added to T H 100 parts by volume of concentrated sulfuric acid. After Ll N cooling off to 0 to 5 C., 36 parts of aqueous nitrosyl- IXLHN 110- sulfuric acid of 40% strength were added and stirred for 1 hour. At a temperature, which shall not exceed 10 C., 200 parts of finely crushed ice were added and [HOSSLB H the nitrosylsulfuric acid in excess was destroyed by a amidosulfonic acid. As no component, an acid solution \X of the sulfuric acid ester of 1(4'-/8-hydroxyethyl-sulfonyl)- phenyl 3- th 1 s-pyrazolone bt i bb b h wherein A represents the benzene or naphthalene radical, reaction of 31.7 parts of (l-(4'- 8-hydroxyethylsulfonyl)- X represents one of the groupings phenyl 3-methyl 5-pyrazolone with 140 parts of concentrated sulfuric acid and decomposition of 1,200 parts 1 of ice) was added and neutralized with 410 parts of anhy- 2 2 drous sodium carbonate. In order to maintain the possiand bility of stirring the coupling mixture at a temperature I?! of about 10 C. a further 2 000 parts of ice were added N so CH CH i durlng the process of neutrallzation. The obtained dyestuif 2 2 a was then salted out with 15% of potassium chloride in which R represents hydrogen or lower alkyl, 11 the in- (referred to the reaction volume). As free acid it correteger 0 or 1, and Z represents sulfato, thiosulfato or disponds to the formula lower alkylamino, Y and Y represent hydrogen, lower alkyl, lower alkoxy, carboxyl, nitro, sulfamido, carb-lower-alkoxy, N,N-di-lower alkyl sulfamido, chlorine, bromine or acetylarnido, R represents lower alkyl, carboxy or carb-loWer-alkoxy, m stands for an integer from 0 to 3, 111 for the integer 0 or 1, the sum of m and m being at most 3, p and p stand for the integers 0 or 1, the sum of p and p being at least 1.

2. A dyestufi as claimed in claim 1, having the formula SOg-CHgCHzO-SO H 3. A dyestufi as claimed in claim 1 having the formula l SOz-CI-I -CH;OSO3H 4. A dyestuif as claimed in claim 1, having the formula 5. A dyestuff as claimed in claim 1 having the formula C N=N-C O O H HaC1TI N/ Hol i SI 0: f

6. A dyestuff as claimed in claim 1 having the formula 

